Metallized bag for static protection of electronic components

ABSTRACT

A flexible sheet material and bags made therefrom for packaging electrostatically sensitive items such as electronic circuit boards. The sheet has a metal layer and an antistatic layer. The outer surface of the bag has a high non-conductive surface resistivity greater than or equal to 10 8  ohms/square, yet the bag protects the packaged item from static voltage by preventing the capacitive coupling of the voltage through the bag to the item packaged therein.

FIELD OF THE INVENTION

The invention relates to metallized flexible laminate films, and bags made therefrom for packaging and protecting static sensitive devices, i.e. electronic components such as circuit boards. The bags provide excellent protection from the discharge of electrical voltage, not allowing it to couple to an electronic component inside the bag. The bag is made of a metal layer and a layer of an antistatic film. The bags work surprisingly well even though the metal side has a relatively high surface resistivity, which is contrary to the teachings of prior patents.

BACKGROUND OF THE INVENTION

Some prior patents on metallized envelopes for protection of electronic components are U.S. Pat. No. 4,154,344 (Parent) and U.S. Pat. No. 4,156,751 (Divisional), both issued to Yenni et al, assignors to 3M. Both patents relate to envelopes having an inside antistatic surface with a surface resistivity of 10⁸ to 10¹⁴ ohms/square, a core insulative sheet with a volume resistivity of at least 10¹⁰ ohm-centimeters, and an outside metal conductive surface with a surface resistivity not greater than 10⁴ ohms/square. The 3M patents and the publicly available file histories thereof teach this metal surface has a surface resistivity of no greater than 10⁴ even if there is a polymeric abrasion protection coating on the metal. For instance, 3M's commercially available 2100 bag has from bag outside to bag inside the structure: nickel/insulative polyester/adhesive/LDPE containing antistat. The nickel bag outside is coated with a thin polymeric abrasion protection coating and still at ambient humidity and temperature the 2100 bag exhibits at ambient conditions on the nickel outside a surface resistivity of 10⁴ ohms/square. Such bags are referred to as "metal out".

Also of interest is U.S. Pat. No. 4,756,414 issued in 1988 to Mott, assignor to Dow Chemical. This patent relates to a bag or pouch having a first and second antistatic layer, which antistat layer is the electron beam radiation cured product as taught by British Published Patent Application 2,156,362 (which is the counterpart of U.S. Pat. No. 4,623,594 issued Nov. 18, 1986 to Keough, assignor to Metallized Products). This electron beam radiation cured antistat film is sold by Metallized Products under the registered trademark Staticure. As per '414, these antistatic layers are bonded along their primary surfaces so that the secondary antistatic surface of one will form the bag outside and the secondary antistatic surface of the other will form the bag inside. At least one primary surface has on it a metal conductive layer, which then due to the sandwiching structure is an internal core of the bag layers. Commercial products like this are referred to as "metal in". For instance, a "metal in" structure is Dow's commercial Chiploc-ES bag, which from the bag outside to the bag inside is of the structure: Staticure/insulative polyester/metal/Staticure/LDPE. Another commercial "metal in" structure is what Fujimori sells as their NONSTAT-PC bag, which from the bag outside to the bag inside is of the structure: antistatic layer/insulative polyester/metal/antistatic layer.

Also of interest is U.S. Pat. No. 4,407,872 issued in 1983 to Horii, assignor to Reiko. This patent relates to an envelope having an outside layer of plastic and an inside metal film layer, the metal having electrical resistance less than 10⁸ ohms/square centimeter. Optionally on the envelope inside is a film layer laminated on the metal film layer for heat-sealing purposes. This also creates a "metal in" sandwich of the structure: plastic layer/metal layer/heat sealing layer.

SUMMARY OF THE INVENTION

Therefore, the present invention provides a flexible sheet material adaptable for forming a package, bag, envelope, or the like, for receiving an electrostatically sensitive item, said sheet material having outer and inner major surfaces, comprising a metallic layer bonded to an antistatic polymeric layer, said antistatic layer defining the inner surface of the package, bag, envelope or the like, said outside surface providing a high non-conductive surface resistivity no less than about 10⁸ ohms/square at ambient conditions of about room temperature and 40 to 60% relative humidity, whereby said metallic layer and said antistatic layer in combination will provide static protection for the electrostatically sensitive item as determined by a capacitive probe test of discharging 1000 volts direct current onto the outer surface, by preventing the voltage from capacitively coupling to the electrostatically sensitive item.

The present invention also provides a method for protecting electrostatically sensitive items from static voltages comprising packaging the item with a flexible sheet material adaptable for forming a package, bag, envelope, or the like, having outer and inner major surfaces, said sheet material having a metallic layer bonded to an antistatic polymeric layer, said antistatic layer defining the inner surface of the package, bag, envelope or the like, said outside surface providing a high non-conductive surface resistivity no less than about 10⁸ ohms/square at ambient conditions of about room temperature and 40 to 60% relative humidity, whereby said metallic layer and said antistatic layer in combination will provide static protection for the electrostatically sensitive item as determined by a capacitive probe test of discharging 1000 volts direct current onto the outer surface, by preventing the voltage from capacitively coupling to the electrostatically sensitive item.

Also, the present invention provides a packaged electrostatically sensitive item protected from electrostatic charges comprising a static sensitive item having conformed thereabout a flexible sheet material adaptable for forming a package, bag, envelope, or the like, for receiving an electrostatically sensitive item, said sheet material having outer and inner major surfaces, said sheet material having a metallic layer bonded to an antistatic polymeric layer, said antistatic layer defining the inner surface of the package, bag, envelope or the like, said outside surface providing a high non-conductive surface resistivity no less than about 10⁸ ohms/square at ambient conditions of about room temperature and 40 to 60% relative humidity, whereby said metallic layer and said antistatic layer in combination will provide static protection for the electrostatically sensitive item as determined by a capacitive probe test of discharging 1000 volts direct current onto the outer surface, by preventing the voltage from capacitively coupling to the electrostatically sensitive item.

Also, the invention optionally provides that on the metallic layer side that is bonded to the antistatic layer, there is a polymeric insulative layer such as polyethylene terephthalate, such that this insulative layer is disposed between the metallic layer and the antistatic layer.

Also optionally provided is that on the outer surface of the metallic layer, there is a second antistatic polymeric layer, such that the metallic layer is sandwiched between the two antistatic layers. There could optionally be an insulative layer diposed between each antistatic layer and the metal so that the resultant is of the structure: antistatic layer/insulative layer/metal/insulative layer/antistatic layer.

Also optionally provided is that the antistatic layer comprises a film of carboxylic acid copolymer and quaternary amine, said film being permanently antistatic.

Accordingly, it is an object of the invention to provide flexible sheet material adaptable for forming a package, bag, envelope, or the like, for receiving an electrostatically sensitive item, whereby the package will prevent the capacitive coupling of voltage through the package outside to the item, when the item is packaged therein, even though the outside of the package has a high, non-conductive surface resistivity of no less than about 10⁸ ohms/square at ambient conditions of about room temperature and 40 to 60% relative humidity. At a "dry" RH of about 15% or less, the surface resistivity on the outside of the package will be no less than about 10¹¹ ohms/square.

DETAILED DESCRIPTION OF THE INVENTION

The laminate of the invention, which may be made into envelopes, bags, pouches, and the like for the packaging of static sensitive devices comprises a thin metal layer laminated to an antistatic layer. This may be accomplished by lamination means such as corona lamination or adhesive lamination, or a combination thereof.

Suitable metals include, but are not limited to, aluminum, stainless steel, copper, nickel, and mixtures thereof. Preferably the thickness of the metal should be not greater than about 300 angstroms (about 0.0012 mil), more preferably less than about 200 angstroms (about 0.00079 mil), most preferably less than about 125 angstroms (about 0.00049 mil). The thinner the metal layer, the more transparent is the finished bag of metal laminated to antistatic layer. Of course, it is more desirable that the bag be transparent enough so that code numbers printed on the circuit board packaged in the bag can be read.

Suitable thicknesses for the antistatic layer are from about 1 mil to 5 mils (25 microns to 125 microns), preferably about 2 to 4 mils (50 to 100 microns). Any antistatic film will work for the antistatic layer. Preferred, however, are the permanent antistatic films of quaternary amine antistatic agent in a polymer containing carboxylic moieties, such as in ethylene acrylic acid copolymer (EAA) or in ethylene methacrylic acid copolymer (EMAA), as shown in U.S. Pat. application Ser. No. 143,885 (Parent) and U.S. Ser. No. 249,488 (Continuation-in-Part), both to Havens and Roberts, assignors to W. R. Grace & Co.-Conn., the disclosures of which are incorporated herein by reference. These two were combined for one foreign filing and their publicly available counterpart is European Patent Application Publication No. 0324494 published in European Patent Bulletin No. 1989/29, on Jul. 19, 1989. The U.S. Applications and EP Publication 0324494 disclose a film, which film has permanent, non-bleeding antistatic characteristics. By "permanent, non-bleeding" antistatic characteristics is meant the film exhibits a static decay time (hereinafter abbreviated as SDT) under about 3000 milliseconds (hereinafter abbreviated as ms) when the static decay test using 5000 volts direct current (hereinafter abbreviated as Vdc) is performed as per Federal Test Method 101c, Method 4046.1, after a 24-hour water shower, i.e. the antistat property is not washed out by the shower. In the preferred embodiments, the film will also still have this SDT of about 3000 ms or less even after 12 days in a hot (approximately 70° to 71° C.) oven. This antistatic film is preferably of 5 plies or layers, each ply containing the quaternary amine antistatic agent, which 5-ply film is commercially available as EPG-112 from the Cryovac Division of W. R. Grace & Co.-Conn. Optionally, an alternative version of EPG-112 having one or more antistat-free layers or plies may be laminated to the metal. For instance, this version may have an antistat-free surface, wherein EPG-112 has been made with a surface ply free of antistat, this surface ply being a polyolefin. Suitable polyolefins for the one or more antistat-free plies include, but are not limited to, low density polyethylene (LDPE), linear low density polyethylene (LLDPE), ethylene-vinyl acetate copolymer (EVA), high density polyethlyene (HDPE), and the like, or mixtures thereof.

Between the metal layer and the antistatic layer, optionally there may be a polymeric insulative layer, such as a layer of polyethylene terephthalate (PET) or its glycol modified derivative (PETG), or of nylon. This insulative layer should be bout 0.2 to 1 mil (about 5.08 to 25.4 microns) thick, preferably about 0.3 to 0.7 mil (about 7.62 to 17.78 microns) thick. Suitable laminates of aluminum metallized polyethylene terephthalate are commercially available from companies such as Scharr or National Metallizers, which aluminum metallized PET can then be laminated to EPG-112 (or laminated to an alternative version of EPG-112). The commercially available laminates of metallized PET are typically made by sputter deposition or vacuum deposition of the metal onto the PET. If the optional insulative layer is not desired, the metal could be vacuum deposited or sputter deposited directly onto the EPG-112 (or to an alternative version of EPG-112).

As per U.S. Ser. Nos. 143,885 and 249,488 and their counterpart EP Publication 0324494, the polymer containing carboxylic acid moieties and the quaternary amine are combined by mixing with heat. Optionally, a polymer compatible therewith, such as a polyolefin, may be blended in the mixture. Any suitable mixing means may be employed such as a blender or a twin screw extruder. The heat should be from about 50° C. to 290° C., more preferably about 100° C. to 250° C., even more preferably about 100° C. to 200° C. Then the resultant may be formed into a film such as by heat pressing on a platen or by any well known extrusion methods. The film is permanently antistatic, which means it will dissipate an applied charge of ±5000 Vdc in less than about 3000 ms, more preferably less than 2000 ms, using the static decay time (SDT) method described in Federal Test Method Standard 101c, Method 4046.1, even after a 24 hour water shower. This is unlike prior polymeric films containing an antistatic agent to give them antistatic characteristics, which characteristics can be washed out after a 24 hour water shower because the agents operate by migrating to the surface and attracting moisture. Furthermore, in some embodiments, the films survive 1 day, more preferably 3 days, even more preferably 5 days, and most preferably 12 days in a hot oven at approximately 70° C. to 71° C. and still exhibit this static decay time (SDT) of less than about 3000 ms, more preferably less than about 2000 ms.

Measuring the antistatic property of the antistatic polymeric film: The antistatic property is exhibited by the ability of a polymer containing an antistatic agent to promote static charge decay, i.e. to dissipate a static charge. The polymer alone will not dissipate a static charge, but the polymer containing the agent is able to dissipate 99% of an applied static charge of ±5000 volt potential in a short amount of time, i.e. less than 3 seconds, more preferably less than 2 seconds (2000 milliseconds). Milliseconds is abbreviated herein as ms. Federal Test Method Standard 101C, Method 4046.1, "Electrostatic Properties of Materials" states less than 2000 ms and thus it is preferred to have a material that complies with 101C. Decay meters for measuring the time for dissipation of the applied volts are commercially available, such as the 406C static decay meter supplied by Electrotech Systems, Inc. Unless otherwise indicated in the Examples below, the films, prior to testing, were equilibrated at less than about 15% relative humidity (RH), which is considered to be a " dry" atmosphere, at about room temperature (RT) for about 24 to 48 hours. For clarity, it is noted that for metallized films, the SDT test is not relevant. Due to the presence of the metal layer, the SDT will be less than 10 ms, which is statisticly insignificant and can be considered as being 0 ms. The appropriate test for metallized films is measuring discharge to ground, as further discussed below.

Measuring resistivity: Some of the films (both metallized and not metallized) were tested for surface resistivity and volume resistivity according to ASTM D257. It is noted that there is not necessarily a correlation between the surface or volume resistivity of a polymeric film and the ability of a polymeric film to decay or dissipate charges as per the SDT test. Thus, the term "antistatic" as used herein describes a material which can dissipate 99% of an applied static charge of ±5000 Vdc in a short amount of time, preferably a static decay time less than about 3 seconds, more preferably less than about 2 seconds (Federal Test Method Standard 101c, Method 4046.1, "Electrostatic Properties of Materials"). If the material also happens to have an antistatic resistivity, i.e. a surface resistivity of about 10⁵ to 10¹² ohms/square as further described below, then that material will be described using the term "antistatic surface resistivity".

The Department of Defense and the Electronics Industry Association have standards on surface resistivity of a material in ohms/square as follows:

    ______________________________________     Surface Resistivity Ranges (ohms/square)     Insulative Antistatic or Static Dissipative                                   Conductive     ______________________________________     >10.sup.12 10.sup.12 to 10.sup.5                                   <10.sup.5     ______________________________________

In the Examples, resistivity was measured at a "dry" relative humidity under about 15% RH, unless indicated that it was measured at an ambient 40 to 60% RH. It is noted that some of the 5-ply films as illustrated by U.S. Ser. Nos. 143,885 and 249,488 and their counterpart EP Pub. 0324494 have both a preferred static decay time of about 3000 milliseconds or less and a static dissipative (as opposed to insulative) surface resistivity of 10¹² to 10⁵ ohms/square, even after a 24-hour water shower or after 12 days in a hot oven. Thus these 5-layer films are permanently antistatic by the definition of static decay time and permanently antistatic by the definition of antistatic surface resistivity; neither the 24-hour water shower nor the 12-day hot oven takes out the "antistatic" characteristic.

Measuring Discharge to Ground; Old Capacitive Probe Test (Human Finger): The old capacitive probe (human finger) method is what 3M used for determining whether an electrical charge will pass through a sheet material and couple to an electronic component. This is in the same 132 affidavit with test data which is publicly available in both file wrappers for each of the 3M U.S. Pat. Nos. 4,154,344 and 4,156,751 to Yenni et al. The method of 3M's test employed a finger of a charged human and thus is less sensitive than the present test method which employs a discharge probe as described below. Although the same charge coupling is measured, use of a human is less sensitive than a discharge probe because interference will occur from such things a whether the human has eaten salty food, whether the human is wearing rubber soled shoes, whether the human is sweaty, and the like.

The 132 affidavit test data compared 3M's bag with a nickel outside, a comparative metallized Atomic Energy Commission bag, and a comparative antistatic Richmond bag. The AEC bag consisted of a sputtered layer of chromium on a sheet of plain 1/2 mil polyester which chromium was overcoated with 510 Angstroms of SiO to provide a surface resistivity of 1.2×10⁵ ohms/square. The Richmond bag consisted of a non-conductive polymeric sheet having coated on both surfaces an antistatic material. 3M placed inside each bag a double sided printed circuit board having two conductive copper plates separated by a layer of insulated material. Wire leads were attached both to the plates of the circuit board and to the inputs of a dual trace oscilloscope through two matched 100 megaohm 3 picofarad one thousand to one high voltage probes so that the effective channel isolation from ground of the leads was on the order of 10⁷ ohms. Then the scope was adjusted so the voltage difference between the two plates on the printed circuit board was displayed and stored on the screen of the scope. The double sided printed circuit board employed was measured as having a total capacitance of 250 picofarads. The source for the electrostatic charge used in the test was a person having a body capacitance of 350 picofarads. The person was charged to a static electrical potential of about 3000 volts for each test. The bag with the circuit board inside was supported on a wooden bench as ground. The charged person discharged himself onto the test bag by placing one finger firmly onto the top of the bag adjacent the top plate of the enclosed circuit board. The scope showed that (1) for the bag of the 3M invention, no voltage pulse measurable by this test was coupled to the printed circuit board inside the bag, (2) for the Richmond bag, a voltage pulse of about 100 volts was coupled to the printed circuit board inside the bag, and (3) for the Atomic Energy Commission bag, a voltage pulse of about 95 volts was coupled to the printed circuit board inside the bag. Thus 3M's bags gave protection against static electrical charges on persons handling the bags to electronic components in the bags of the type sought to be protected, and the bags of the type acknowledged as prior art (AEC and Richmond) with the 95 to 100 volts did not. The Yenni et al patents state 3M's nickel metallized bag has a surface resistivity on the nickel outside of 10⁴ ohms/square.

Measuring Discharge to Ground; Present Capacitive Probe Test (Test Fixture): The present method for determining whether an electrical charge will pass through a sheet material and couple to an electronic component is a variation of EIA-541 Appendix E. An Electro-Tech Systems, Inc. shielded bag test fixture Model 402 is fitted with a capacitor of about 25 picofarads which is placed inside a metallized bag. The capacitor simulates an electronic component such as a circuit board that would be stored inside the bag. The bag rests on an aluminum ground plate. Next, an Electro-Tech Systems Model 881 power supply is adjusted to 1000 volts. Then the 1.5 kilo-ohm discharge probe of the test fixture is lowered onto the bag. The capacitor is connected with leads through the test fixture which leads are connected to a 141A oscilloscope from Hewlett-Packard using a 1402 dual trace amplifier, DC 20 MHz. A reading of a few volts, say 10 or less, is statistically insignificant (as this new test is more sensitive than the old human finger method) and considered to be 0 volts and shows the bag performs well.

The following examples are intended to illustrate the invention and it is not intended to limit the invention thereby.

EXAMPLE I Laminate of Aluminum Metallized PET to EPG-112.

EPG-112 was a coextruded, hot blown, 5-layer symmetric film of the structure: A/B/C/B/A made in thicknesses of 2.0, 3.0, and 4.0 mils, where the percentages recited below were in % by weight.

    ______________________________________     Layer A: Composed of EVA, EAA, antiblock, antistatic agent     EVA: 30% of Layer A     Density:           0.929 to 0.931 g/ml     VA Content:        9.0 ± 0.5%     Melt Index:        1.8 to 2.2 g/10 min.,                        ASTM D-1238     EAA: 52.5% of Layer A     Density:           0.938 g/ml     Acrylic Acid Content:                        9.5%     Vicat Softening Point:                        180° F.     Melt Index:        1.5 ± 0.5 g/10 min.,                        ASTM D-1238     Antiblock Masterbatch - Silica Dispersion in Polyethylene:     10% of Layer A     Density of Antiblock Masterbatch:                        0.96 to 0.98 g/ml     Melting Point of Masterbatch:                        Unknown     Silica Content:    10%     Melt Index of Masterbatch:                        3.90 to 4.14 g/10 min.,                        ASTM D-1238     Antistat: Modified Soya Dimethylethlammonium Ethosulfate:     7.5% of Layer A     Density of Antistat:                        1.005 g/ml @ 25° C.     pH 35% Solution in Water:                        6.0-6.9 @ 25° C.     Boiling Point:     >300° F.     Melting Point:     120° F.     Layer B: Composed of EVA, EAA, and Antistatic Agent     EVA: 67% of layer B     Same EVA as layer A     EAA: 24.7% of layer B     Same EAA as layer A     Antistatic Agent: 8.3% of layer B     Same antistatic agent as layer A     Layer C: Composed of LLDPE, EAA, Antistatic Agent     LLDPE: 90% of layer C     Density:           0.918 to 0.922 g/ml     Melting Point:     123-126° C., DSC 2nd heat     Melt Index:        1.1 ± 1 g/10 min.     Octene Comonomer Content:                        6.5 ± 0.5%     EAA: 7.5% of layer C     Same EAA as layer A     Antistatic Agent: 2.5% of layer C     Same antistatic agent as layer A     ______________________________________

4 mil EPG-112 was then adhesively laminated to Scharr's commercially available 48 gauge (0.48 mil) aluminum metallized polyester on the polyester side, using a polyurethane adhesive (the polyurethane adhesive is commercially available under the tradename Korolam 880X301 or Korolam 880X388 from DeSoto Chemical, Chicago Heights, Ill.), to make a laminate of the structure: aluminum/polyester/adhesive/antistatic film. Bags were made by heatsealing together on three edges two sections of the laminate with the antistatic film side being the sealing layer. Bags were sufficiently transparent to afford visual identification of an electrical component inside the envelope or bag.

Results of electrical measurements at room temperature on the laminate of aluminum/polyester/antistatic EPG-112, as well as on EPG-112 and on the metallized polyester were as follows (NT designates the particular measurement was not tested):

    ______________________________________            Aluminum Side            60% RH  12% RH    60% RH    12% RH*     ______________________________________     Laminate             Antistatic Film Side     surface  1 × 10.sup.8                        7.0 × 10.sup.11                                  7.8 × 10.sup.9                                          3.7 × 10.sup.11     resistivity     ohms/sq     volume   4.7E11    NT        1.7 × 10.sup.13                                          5.6 × 10.sup.16     resistivity     ohms-cm     SDT ms   NT        NT        NT      less than 10     EPG-112              Antistatic Film     surface              NT        3 × 10.sup.11     resistivity     ohms/sq     SDT ms               NT        450     Metallized     Polyester            Polyester Side     surface  1 × 10.sup.8                        NT        off     NT     resistivity                  scale**     ohms/sq     volume   3 × 10.sup.14                        NT        off     NT     resistivity                  scale     ohms-cm                          ***As Reported in                          Modern Plastics     PET                  Encyclopedia     surface              >10.sup.14     resistivity     ohms/sq     volume               >10.sup.16     resistivity     ohms-cm     ______________________________________      *RH is an abbreviation for relative humidity. A moist humid atmosphere      increases conductivity. Thus at a "humid" ambient 40 to 60% RH,      resistivity should be lower than at a "dry" atmosphere of 12% RH. Since      the 3M patents are silent about RH of resistivity test conditions, it was      assumed their tests were performed at an ambient 40 to 60% RH. Thus, our      tests were performed our way at "dry" 12% RH and also repeated at an      "ambient" 60% RH. Our tests confirmed that increased humidity decreases      resistivity.      **The maximum meter scale reads to 10.sup.16. Thus, off scale means a      resistivity of at least 10.sup.16.      ***It is not possible to pull the polyester cleanly off the aluminum to      obtain a reading on polyester alone; therefore, reported measurements on      PET were taken from the Encyclopedia, 1985-86, page 563, vol. 62, Schulma      (Supplier), Arnite (tradename for polyethylene glycol terephthalate).

This adhesive lamination of the EPG-112 to the aluminum metallized polyester was also repeated by adhesively laminating the aluminum side (as opposed to the PET side) of the PET/aluminum to EPG-112. Surface resistivity on the PET side was 3.4×10¹² ohms/square.

EXAMPLE II

Another metallized laminate with 5-layer antistatic film was made as in Example I using 48 gauge (0.48 mil) aluminum metallized PET commercially available from Scharr, which was corona treated and then adhesively laminated with polyurethane adhesive to an alternative version of EPG-112. In the alternative, 1 of the 5 layers of EPG-112, a surface layer, was instead of ethylene-vinyl acetate copolymer free of any quaternary amine antistatic agent. The EVA was commercially available from Rexene. The EVA side was laminated to the PET side of the PET/aluminum. Surface resistivity on the aluminum side was 4.1×10¹¹.

This was also repeated by instead laminating the aluminum side of the PET/aluminum to the EVA surface of the 5-ply antistatic film. Surface resistivity on the PET side was off scale.

EXAMPLE III

Another metallized laminate with 5-layer antistatic film was made as in Example I using 48 gauge (0.48 mil) aluminum metallized PET commercially available from Scharr, which was corona treated and then adhesively laminated with polyurethane adhesive to an alternative version of EPG-112. In the alternative, 1 of the 5 layers of EPG-112, a surface layer, was instead of ethylene-vinyl acetate copolymer free of any quaternary amine antistatic agent. The EVA was commercially available from Exxon. The EVA side was laminated to the PET side of the PET/aluminum. Surface resistivity on the aluminum side was 2.4×10¹¹.

This was repeated by instead laminating the aluminum side of the PET/aluminum to the EVA surface of the 5-layer antistatic film. Surface resistivity on the PET side was 7.8×10¹².

EXAMPLE IV

Laminates are made similar to those in Example I, but this time they are of the "metal in" type, where the aluminum is a buried core layer between antistatic film on each side thereof. These are of the structure:

EPG-112/Adhesive/Aluminum/PET/Adhesive/EPG-112

EXAMPLE V

Laminates are made of the "metal in" type as in Example IV, but using the alternative version of EPG-112 as per Example II that has an EVA surface. This is, on its EVA surface, laminated to each side of the aluminum/PET to make laminates of the structure:

Antistatic Film/Adhesive/Aluminum/PET/Adhesive/Antistatic Film

EXAMPLE VI

Laminates are made of the "metal in" type as in Example IV, but using the alternative version of EPG-112 as per Example III that has an EVA surface. This is, on its EVA surface, laminated to each side of the aluminum/PET to make laminates of the structure:

Antistatic Film/Adhesive/Aluminum/PET/Adhesive/Antistatic Film

COMPARATIVE EXAMPLE VERSUS EXAMPLE I

A bag of the structure from outside to inside: aluminum/PET/adhesive/EPG-112 as per Example I was compared to 3M's commercially available 2100 metalized bag of the structure: nickel/insulative polyester/adhesive/LDPE containing antistat. The 2100 bag has been advertised as having a thin polymeric abrasion protection coating on the nickel outside surface of the bag, and also advertised as having a surface resistivity at ambient conditions on this nickel outside surface of 10⁴ ohms/square. Not greater than 10⁴ ohms/square also is what is claimed in the above mentioned 3M U.S. Pat. Nos. 4,154,344 and 4,156,751 to Yenni et al. In contrast, as can be seen in above Example I, the aluminum/PET/adhesive/EPG-112 had on its aluminum outside surface at ambient conditions a surface resistivity of 1×10⁸ ohms/square at ambient RH, and about 7×10¹¹ ohms/square at a "dry" 12% RH. Although it is not exactly known why and it is not intended to be bound to any theory, it is theorized that this occurred because aluminum, when exposed to air, quickly forms an insulator of Al₂ O₃, and thus due to the presence of the Al₂ O₃, the bag outside gave a reading of 1×10⁸.

Next, a capacitive probe test was performed on both the bag of the structure from outside to inside: aluminum/PET/adhesive/EPG-112 made as per Example I and the 3M 2100 bag with the new method of the Electro-Tech Systems shielded bag test fixture Model 402, not the old human finger method. The Example I bag provided readings ranging from 4 to 6 volts, whereas the commercially available 3M 2100 bag provided readings ranging from 2 volts to 4 volts. As mentioned above, this new method is more sensitive than the old human finger method. Thus, these small voltages are not statistically significant and can be considered as a 0 voltage reading when using the old human finger test method.

This data is summarized in the Table below as follows:

                  TABLE     ______________________________________               Surface Resistivity                              Capacitive               Ohms/Square on Probe Test     Sample    Metal Outside Surface                              Voltage Read on Scope     ______________________________________     Aluminum/ 1 × 10.sup.8                              4 to 6     PET/EPG-112     3M's 2100 10.sup.4       2 to 4     ______________________________________

Accordingly, the material of the instant invention clearly protected a static sensitive device (the capacitive probe test was excellent) even though the material had a high surface resistivity of 10⁸, clearly beyond the not greater than 10⁴ taught by the 3M patents.

While certain representative embodiments and details have been shown for the purpose of illustration, numerous modifications to the formulations described above can be made without departing from the invention disclosed. 

What is claimed is:
 1. A flexible sheet material adaptable for forming a package, bag, or envelope for receiving an electrostatically sensitive item, said sheet material having outer and inner surfaces, comprising an aluminum metallic layer bonded to an antistatic polymeric layer, said antistatic layer defining the inner surface of the package, bag, or envelope, said outside aluminum metallic surface, due to the presence of Al₂ O₃ on said outside aluminum metallic surface, providing a high non-conductive surface resistivity no less than about 10⁸ ohms/square at ambient conditions of about room temperature and 40 to 60% relative humidity, whereby said aluminum metallic layer and said antistatic layer in combination will provide static protection for the electrostatically sensitive item as determined by a capacitive probe test of discharging 1000 volts direct current onto the outer surface, by preventing the voltage from capacitively coupling to the electrostatically sensitive item.
 2. The sheet material of claim 1, wherein on the metallic layer side that is bonded to the antistatic layer, there is a polymeric insulative layer such as polyethylene terephthalate, such that this insulative layer is disposed between the metallic layer and the antistatic layer.
 3. The sheet material of claim 1 wherein on the outer surface of the metallic layer, there is a second antistatic polymeric layer, such that the metallic layer is sandwiched between the two antistatic layers.
 4. The sheet material of claim 1 wherein the antistatic layer comprises a film of carboxylic acid copolymer and quaternary amine, said film being permanently antistatic.
 5. A method for protecting electrostatically sensitive items from static voltages comprising packaging the item with a flexible sheet material adaptable for forming a package, bag, or envelope, having outer and inner surfaces, said sheet material having an aluminum metallic layer bonded to an antistatic polymeric layer, said antistatic layer defining the inner surface of the package, bag, or envelope, said outside aluminum metallic surface providing, due to the presence of Al₂ O₃ on said outside aluminum metallic surface, a high non-conductive surface resistivity no less than about 10⁸ ohms/square at ambient conditions of about room temperature and 40 to 60% relative humidity, whereby said aluminum metallic layer and said antistatic layer in combination will provide static protection for the electrostatically sensitive item as determined by a capacitive probe test of discharging 1000 volts direct current onto the outer surface, by preventing the voltage from capacitively coupling to the electrostatically sensitive item.
 6. The method according to claim 5, wherein on the metallic layer side that is bonded to the antistatic layer, there is a polymeric insulative layer such as polyethylene terephthalate, such that this insulative layer is disposed between the metallic layer and the antistatic layer.
 7. The method according to claim 5 wherein on the outer surface of the metallic layer, there is a second antistatic polymeric layer, such that the metallic layer is sandwiched between the two antistatic layers.
 8. The method according to claim 5 wherein the antistatic layer comprises a film of carboxylic acid copolymer and quaternary amine, said film being permanently antistatic.
 9. A packaged electrostatically sensitive item protected from electrostatic charges comprising a static sensitive item having conformed thereabout a flexible sheet material adaptable for forming a package, bag, or envelope, for receiving an electrostatically sensitive item, said sheet material having outer and inner surfaces, said sheet material having an aluminum metallic layer bonded to an antistatic polymeric layer, said antistatic layer defining the inner surface of the package, bag, or envelope, said outside aluminum metallic surface providing, due to the presence of Al₂ O₃ on said outside aluminum metallic surface, a high non-conductive surface resistivity no less than about 10⁸ ohms/square at ambient conditions of about room temperature and 40 and 60% relative humidity, whereby said aluminum metallic layer and said antistatic layer in combination will provide static protection for the electrostatically sensitive item as determined by a capacitive probe test of discharging 1000 volts direct current onto the outer surface, by preventing the voltage from capacitively coupling to the electrostatically sensitive item.
 10. The packaged item of claim 9, wherein on the metallic layer side that is bonded to the antistatic layer, there is a polymeric insulative layer such as polyethylene terephthalate, such that this insulative layer is disposed between the metallic layer and the antistatic layer.
 11. The packaged item of claim 9 wherein on the outer surface of the metallic layer, there is a second antistatic polymeric layer, such that the metallic layer is sandwiched between the two antistatic layers.
 12. The packaged item of claim 9 wherein the antistatic layer comprises a film of carboxylic acid copolymer and quaternary amine, said film being permanently antistatic. 